WO2015068682A1 - Active energy ray-curable composition, cured product thereof, and article having cured coating film thereof - Google Patents
Active energy ray-curable composition, cured product thereof, and article having cured coating film thereof Download PDFInfo
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- WO2015068682A1 WO2015068682A1 PCT/JP2014/079198 JP2014079198W WO2015068682A1 WO 2015068682 A1 WO2015068682 A1 WO 2015068682A1 JP 2014079198 W JP2014079198 W JP 2014079198W WO 2015068682 A1 WO2015068682 A1 WO 2015068682A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention provides an active energy ray-curable composition capable of imparting high pencil hardness to the surface of various articles, and further imparting excellent scratch resistance, antifouling property, and slipperiness, a cured product thereof, and a cured coating film thereof. It relates to an article having.
- the active energy ray-curable composition has a low heat history to the substrate to be applied, and is excellent in coating film hardness and scratch resistance. For example, it is soft and has a defect that the surface is easily damaged. It is used as a hard coat agent that imparts scratch resistance to the surface.
- a fluorine compound having a perfluoropolyether group and a polymerizable group is proposed as a material to be added to the active energy ray curable composition. (For example, refer to Patent Document 1).
- the cured coating film of the active energy ray-curable composition to which the fluorine compound described in Patent Document 1 is added has a problem that it is inferior in scratch resistance, pencil hardness and slipperiness although it has excellent antifouling properties. Accordingly, there has been a demand for an active energy ray-curable composition that can provide a cured coating film that has excellent antifouling properties and is excellent in scratch resistance, pencil hardness, and slipperiness.
- the problem to be solved by the present invention is an active energy ray-curable composition that has a high pencil hardness, and further provides a cured coating film having excellent scratch resistance, antifouling properties, and slipperiness, a cured product thereof, and It is to provide an article having the cured coating.
- the present inventors have made active energy ray curing in which a fluorine compound having a specific structure, reactive silica and non-reactive silica are added to the active energy ray curable compound.
- the surface of the cured coating film of the adhesive composition has high pencil hardness, and further has excellent scratch resistance, antifouling property, and slipperiness, and the present invention has been completed.
- a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure is bonded to the cyclopolysiloxane structure.
- Active energy comprising a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded via a divalent linking group, reactive silica (C1), and non-reactive silica (C2)
- the present invention relates to a linear curable composition, a cured product thereof, and an article having the cured coating film. Furthermore, this invention relates to the protective film which provided the hard-coat film which used the hardened
- the active energy ray-curable composition of the present invention has a surface of various articles because the surface of the cured coating film has high pencil hardness and excellent scratch resistance, antifouling property, and slipperiness. It is extremely useful as a hard coat agent for protection.
- a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group
- a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded to the cyclopolysiloxane structure through a divalent linking group
- (meth) acrylate refers to one or both of acrylate and methacrylate
- (meth) acryloyl group refers to one or both of acryloyl group and methacryloyl group.
- Examples of the active energy ray-curable compound (A) include urethane (meth) acrylate and polyfunctional acrylate.
- (A1) is composed of four or more (meta) in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a (meth) acrylate (a2) having a hydroxyl group. ) It has an acryloyl group.
- the aliphatic polyisocyanate (a1) is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon.
- Specific examples of the aliphatic polyisocyanate (a1) include aliphatic polyisocyanates (a1-1) such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), Alicyclic polyisocyanates (a1-2) such as 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc.
- a trimerization product obtained by trimming the aliphatic polyisocyanate (a1-1) or the alicyclic polyisocyanate (a1-2) can also be used as the aliphatic polyisocyanate (a1).
- aliphatic polyisocyanates (a1) hexamethylene diisocyanate, which is a diisocyanate of linear aliphatic hydrocarbons, norbornane diisocyanate, which is an alicyclic diisocyanate, and isophorone diisocyanate are those of the active energy ray-curable composition of the present invention. It is preferable because the pencil hardness and scratch resistance on the surface of the cured coating film can be further improved.
- the (meth) acrylate (a2) is a compound having a hydroxyl group and a (meth) acryloyl group, but the urethane (meth) acrylate (A1) has four or more (meth) acryloyl groups in one molecule. Therefore, it is preferable to have two or more (meth) acryloyl groups.
- (meth) acrylate (a2) for example, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, glycerin di (Meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. .
- (meth) acrylates (a2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates (a1).
- pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are pencil hardnesses on the surface of the cured coating film of the active energy ray-curable composition of the present invention. And scratch resistance can be further improved.
- the reaction between the aliphatic polyisocyanate (a1) and the (meth) acrylate (a2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
- urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
- the urethane (meth) acrylate (A1) obtained by the above urethanization reaction can be used alone or in combination of two or more. Moreover, when using 2 or more types, the urethane acrylate obtained using hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) and the trimer of hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) are used.
- the combined use with the obtained urethane acrylate is preferable because the pencil hardness and scratch resistance of the cured coating film surface of the active energy ray-curable composition of the present invention can be further improved.
- the polyfunctional (meth) acrylate (A2) is a compound having three or more (meth) acryloyl groups in one molecule.
- Specific examples of the polyfunctional (meth) acrylate (A2) include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrile.
- polyfunctional (meth) acrylates (A2) can be used alone or in combination of two or more.
- the (meth) acryloyl group The equivalent weight is 50 to 200 g / eq. In the range of 70 to 150 g / eq. In the range of 80 to 120 g / eq. The thing of the range is more preferable.
- the (meth) acryloyl group equivalent is 80 to 200 g / eq.
- polyfunctional (meth) acrylate (A2) in the range of 5 are pentaerythritol tetraacrylate (acryloyl group equivalent: 88 g / eq.), Dipentaerythritol hexaacrylate (acryloyl group equivalent: 118 g / eq.), And the like. Is mentioned.
- the mass ratio [(A1) / (A2)] of the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2) can improve the scratch resistance, 90/10 to 10/90
- the range of 80/20 to 20/80 is more preferable, and the range of 75/25 to 25/75 is more preferable.
- the active energy ray-curable composition of the present invention includes one molecule within a range not impairing the effects of the present invention, in addition to the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2).
- Other (meth) acrylates such as mono (meth) acrylate having one (meth) acryloyl group in it and di (meth) acrylate having two (meth) acryloyl groups in one molecule may be blended.
- the blending amounts thereof are the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2). 40 parts by mass or less is preferable with respect to a total of 100 parts by mass, and 20 parts by mass or less is more preferable.
- the fluorine compound (B) has a cyclopolysiloxane structure bonded to both ends of the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure via a divalent linking group. It is a compound having a structure in which a (meth) acryloyl group is bonded.
- poly (perfluoroalkylene ether) is sometimes referred to as “perfluoropolyether”.
- Examples of the poly (perfluoroalkylene ether) chain of the fluorine compound (B) include those having a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately connected.
- the divalent fluorinated carbon group having 1 to 3 carbon atoms may be one kind or a combination of two or more kinds. Specific examples include those represented by the following structural formula (1). It is done.
- X is the following formulas (1-1) to (1-5), and X is one of the following formulas (1-1) to (1-5)
- two or more of the following formulas (1-1) to (1-5) may be present in a random or block form, and n represents a repeating unit. Represents an integer of 2 to 200.
- the perfluoromethylene represented by the formula (1-1) is used.
- a poly (perfluoroalkylene ether) chain in which a group and a perfluoroethylene group represented by the formula (1-2) are combined is preferable.
- the molar ratio of the perfluoromethylene group represented by the formula (1-1) to the perfluoroethylene group represented by the formula (1-2) [(1-1) / (1-2 )] Is preferably in the range of 1/10 to 10/1.
- the value of n in the general formula (1) is preferably in the range of 2 to 200, more preferably in the range of 10 to 100, and further preferably in the range of 20 to 80.
- Examples of the cyclopolysiloxane structure possessed by the fluorine compound (B) include a structure represented by the following general formula (2).
- R 1 is a methyl group
- R 3 is a divalent organic group bonded to a poly (perfluoroalkylene ether) chain
- R 4 is a 1 having a (meth) acryloyl group.
- m is an integer of 2 to 5.
- cyclopolysiloxane structures a cyclotetrasiloxane structure in which m in the general formula (2) is 3 is preferable.
- the divalent linking group that connects the poly (perfluoroalkylene ether) chain and the cyclopolysiloxane structure is not particularly limited as long as it is a divalent organic group.
- the divalent linking group is represented by the following general formula (3). Can be mentioned.
- Y is an alkylene group having 1 to 6 carbon atoms.
- the divalent linking group that bonds the cyclopolysiloxane structure and the (meth) acryloyl group is not particularly limited as long as it is a divalent organic group.
- it is represented by the following general formula (4). Things.
- Z 1 , Z 2 and Z 3 are each independently an alkylene group having 1 to 6 carbon atoms.
- Examples of the method for producing the fluorine compound (B) include a method for producing the fluorine compound (B) through the following steps (1) to (3).
- a compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain and a cyclopolysiloxane compound having a hydrosilyl group are reacted in the presence of a platinum-based catalyst to form both poly (perfluoroalkylene ether) chains.
- the blending amount of the fluorine compound (B) in the active energy ray-curable composition of the present invention can impart higher pencil hardness to the cured coating film surface of the active energy ray-curable composition of the present invention, and scratch resistance.
- the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended in a total of 100 parts by mass
- the range of 0.05 to 5 parts by mass is preferable, and the range of 0.1 to 2 parts by mass is more preferable.
- the reactive silica (C1) is obtained by introducing a reactive group such as a (meth) acryloyl group on the surface of silica particles by surface modification.
- the reactive silica (C1) is preferably nanometer-sized, since it can further improve the transparency of the cured coating film of the active energy ray-curable composition of the present invention and the pencil hardness of the surface.
- Silica is preferred.
- the specific average particle size is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm.
- the non-reactive silica (C2) does not have a reactive group on the surface of the silica particles, but may be surface-modified with a non-reactive organic group. Further, the non-reactive silica (C2) can further improve the transparency of the cured coating film and the pencil hardness of the surface of the active energy ray-curable composition of the present invention, and can further improve the curl resistance.
- An order size is preferable, and colloidal silica is preferable.
- the specific average particle size is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm.
- the use ratio [(C1) / (C2)] of the reactive silica (C1) and the non-reactive silica (C2) is the pencil hardness of the cured coating film surface of the active energy ray-curable composition of the present invention.
- the range of 0.5 to 1.5 is preferable, and the range of 0.6 to 1 is more preferable.
- the total amount of the reactive silica (C1) and the non-reactive silica (C2) in the active energy ray-curable composition of the present invention is the amount of the cured coating film surface of the active energy ray-curable composition of the present invention. Since the pencil hardness, scratch resistance, antifouling property and slipperiness can be further improved, the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended Is preferably in the range of 100 to 300 parts by mass, more preferably in the range of 150 to 280 parts by mass.
- the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate.
- the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- a photopolymerization initiator (D) is added to the active energy ray curable composition of the present invention to improve curability.
- a photosensitizer can be further added to improve curability.
- Examples of the photopolymerization initiator (D) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators.
- Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone], benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as
- the hydrogen abstraction type photopolymerization initiator includes, for example, benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide.
- the photosensitizer examples include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothuronium-p. -Sulfur compounds such as toluene sulfonate.
- tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
- urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothuronium-p.
- -Sulfur compounds such as toluene sulfonate.
- the amount of these photopolymerization initiator and photosensitizer used is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. More preferred is 15% by mass.
- the active energy ray-curable composition of the present invention includes a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity as necessary.
- Additives such as regulators, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads; silicon oxide, oxidation Inorganic fillers such as aluminum, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
- the method for applying the active energy ray-curable composition of the present invention to the substrate varies depending on the application, but includes, for example, die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, Examples include dip coating, spinner coating, wheeler coating, brush coating, full surface coating with silk screen, wire bar coating, and flow coating.
- the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- the sources of ultraviolet rays are low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, electrodeless lamps, chemical lamps, black light lamps, mercury-xenon. Examples include lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, and LEDs.
- the substrate to which the active energy ray-curable composition of the present invention is applied is a film substrate
- the influence of heat on the film substrate can be reduced by using a flashing xenon-flash lamp. Therefore, it is preferable.
- the generation source of the electron beam include a scanning electron beam accelerator and a curtain type electron beam accelerator.
- the active energy ray-curable composition of the present invention when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a cured coating film, it may be performed in an air atmosphere, but a cured coating film having higher pencil hardness is obtained, Furthermore, it is preferable to carry out in an atmosphere having an oxygen concentration of 5,000 ppm or less because a cured coating film having excellent scratch resistance and slipperiness can be obtained.
- the active energy ray-curable composition of the present invention Since the cured coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties and is excellent in scratch resistance and slipperiness, the active energy ray-curable composition of the present invention is variously used. By applying and curing on the surface of an article, high pencil hardness can be imparted to the surface of various articles, and excellent antifouling properties, scratch resistance and slipperiness can also be imparted. Therefore, the active energy ray-curable composition of the present invention is very useful as a hard coating agent capable of imparting high scratch resistance, antifouling property and the like to the surface of various articles.
- Articles to which the active energy ray-curable composition of the present invention can be applied include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Enclosures; Interior materials for various vehicles such as automobiles and railway vehicles; Various building materials such as decorative panels; Woodwork materials such as furniture; Artificial and synthetic leather; FRP bathtubs; Liquid crystal displays (LCD) such as triacetylcellulose (TAC) films Optical film; Prism sheet or diffusion sheet as backlight member of LCD; Various display screens (hard coat layer, antireflection layer) such as plasma display (PDP) and organic EL display; Touch panel; Electronics such as mobile phones and smartphones Terminal screen: Color filter for liquid crystal display (hereinafter referred to as “CF”) ) Transparent protective film; Optical recording media such as CD, DVD, Blu-ray Disc; Transfer film for insert mold (IMD, IMF); Rubber roller for OA equipment such as copiers and printers
- the hard coat film of the present invention has a hard coat layer obtained by curing the active energy ray-curable composition of the present invention on at least one surface of a film substrate.
- a film substrate various commonly used resin film substrates can be used, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate.
- the film substrate may be a substrate composed only of the resin film mentioned above, but in order to improve the adhesion with the active energy ray-curable composition of the present invention, the resin film It may be a film substrate provided with a primer layer.
- the primer layer include those made of polyester resin, urethane resin, acrylic resin, and the like.
- the surface of the resin film is subjected to surface concavo-convex treatment by sandblasting method, solvent treatment method, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone
- the treatment can also be performed by ultraviolet irradiation treatment, oxidation treatment or the like.
- the thickness of the film substrate is preferably in the range of 50 to 200 ⁇ m, more preferably in the range of 80 to 150 ⁇ m, and still more preferably in the range of 90 to 130 ⁇ m.
- curling can be easily suppressed even when a hard coat layer is provided on one side of the film substrate.
- a film substrate having an elastic modulus in the range of 3 to 7 GPa is preferably used, and a film substrate in the range of 3 to 5 GPa is particularly preferable.
- the elastic modulus is within this range, deformation of the film substrate is less likely to occur when a protective film is formed, and cracking of the hard coat layer can be suppressed, and a decrease in hardness of the hard coat film surface can be easily suppressed.
- the flexibility of the film base material can be ensured, it is easy to follow a gentle curved surface when a protective film described later is attached.
- the protective film of the present invention has an adhesive layer on one side of the hard coat film.
- the pressure-sensitive adhesive layer can be provided by attaching a pressure-sensitive adhesive tape to the film base material, or by directly applying a pressure-sensitive adhesive layer to the surface opposite to the hard coat surface of the film base material.
- the thickness of the pressure-sensitive adhesive layer of the protective film of the present invention is preferably in the range of 5 to 50 ⁇ m, more preferably in the range of 8 to 30 ⁇ m, and even more preferably in the range of 10 to 25 ⁇ m.
- this invention by making the thickness of an adhesive layer into the said range, it is excellent in adhesive reliability, and can maintain the surface hardness of a hard coat film not remarkably impaired.
- the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention known acrylic, rubber-based, silicone-based pressure-sensitive resins can be used.
- an acrylic copolymer obtained by polymerizing a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a repeating unit as a main component has excellent adhesion to a film substrate, transparency, It is preferable from the point of weather resistance.
- Examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and n-hexyl acrylate.
- an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferable, and an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is more preferable.
- an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is more preferable.
- the alkyl acrylates n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are particularly preferable.
- the content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the pressure-sensitive adhesive layer of the present invention is preferably 90 to 99% by mass, More preferably, it is made -96 mass%. By setting the content of the (meth) acrylate in this range, it is easy to ensure a suitable adhesive force.
- (meth) acrylate monomers having polar groups such as hydroxyl, carboxyl and amide groups and vinyl monomers having other polar groups should be used as monomer components. Is preferred.
- Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, Examples include caprolactone-modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate are preferably used.
- Examples of the (meth) acrylate monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid or methacrylic acid dimer, ethylene oxide-modified succinic acid acrylate, and the like. Can be mentioned. Among these, it is preferable to use acrylic acid.
- Examples of the (meth) acrylate monomer having an amide group include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide, N-acryloyloxyethyl-3, 4,5,6-tetrahydrophthalimide and the like. Of these, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloylmorpholine are preferably used.
- Examples of the other vinyl monomers having a polar group include vinyl acetate, acrylonitrile, maleic anhydride, itaconic anhydride and the like.
- the content of the monomer having a polar group is preferably 0.1 to 20% by mass, more preferably 1 to 13% by mass, based on the monomer component constituting the acrylic copolymer. More preferably, it is 1.5 to 8% by weight.
- the weight average molecular weight Mw of the acrylic copolymer used for the pressure-sensitive adhesive layer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000. When the weight average molecular weight Mw of the acrylic copolymer is within the range, it is easy to adjust the adhesive force to a specific range.
- the weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values. (GPC measurement conditions) Sample concentration: 0.5% by weight (tetrahydrofuran solution) Sample injection volume: 100 ⁇ L ⁇ Eluent: Tetrahydrofuran (THF) ⁇ Flow rate: 1.0 mL / min Column temperature (measurement temperature): 40 ° C ⁇ Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation ⁇ Detector: Differential refraction
- a crosslinking agent to the pressure-sensitive adhesive.
- a crosslinking agent an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example.
- the addition amount of the crosslinking agent is preferably adjusted so that the gel fraction of the pressure-sensitive adhesive layer is 25 to 80% by mass, more preferably adjusted to be 40 to 75% by mass, and 50 to 70% by mass. It is most preferable to adjust so that.
- the gel fraction in the present invention is expressed as a percentage of the original mass by immersing the cured pressure-sensitive adhesive layer in toluene, measuring the mass after drying of the insoluble matter remaining after standing for 24 hours, and the original mass. Is.
- a tackifier resin may be added to improve the adhesive strength of the adhesive layer.
- the addition amount of the tackifier resin is preferably in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the acrylic copolymer when the adhesive resin is an acrylic copolymer. Further, when importance is attached to adhesion, it is preferably added in the range of 20 to 50 parts by mass.
- additives can be added to the adhesive.
- the silane coupling agent in the range of 0.001 to 0.005 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive.
- a plasticizer, a softening agent, a filler, a pigment, a flame retardant, etc. can also be added as other additives as needed.
- the protective film of the present invention can be applied to various uses because it has suitable scratch resistance and slipperiness, and is particularly suitable for an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display. Applicable.
- an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display.
- LCD liquid crystal display
- organic EL display an organic EL display.
- portable electronic devices that are highly demanded for miniaturization and thinning of electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It is suitable as a protective film for the image display unit of the terminal image display device.
- an image display device for example, a configuration in which an image display module such as an LCD module or an organic EL module is included in the configuration, and a transparent panel for protecting the image display module is provided above the image display module.
- an image display module such as an LCD module or an organic EL module
- a transparent panel for protecting the image display module is provided above the image display module.
- it is effective to prevent scratches and to prevent scattering when the transparent panel is damaged by being attached to the front or back surface of the transparent panel.
- urethane acrylate (A1-2) having 6 acryloyl groups in one molecule A non-volatile content 80% by mass solution was obtained. This solution contains 19.5% by mass of PE4A in addition to urethane acrylate (A1-2) in the nonvolatile content.
- trimerized hexamethylene diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd.) Module N3390BA ”, 90% by mass of non-volatile content, NCO%: 19.6, NCO equivalent: 214 g / eq.) 107 parts by mass and 50 parts by mass of methyl ethyl ketone were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was reacted at 75 ° C.
- a perfluoropolyether compound (2) which is a pale yellow transparent liquid represented by
- an active energy ray-curable composition was prepared as follows.
- the active energy ray-curable composition (1) obtained above is coated with a wire bar (# 40) on the easy-adhesion treated surface of a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m).
- a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m).
- an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp in an atmosphere having an oxygen concentration of 5,000 ppm or less. )
- MIDN-042-C1 manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp in an atmosphere having an oxygen concentration of 5,000 ppm or less.
- MIDN-042-C1 manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury
- test piece film obtained above was evaluated or measured for the following curls, pencil hardness, scratch resistance, water contact angle, antifouling property, and slipperiness.
- the test piece film obtained above is cut into a 30 cm ⁇ 2 cm rectangle, fixed to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a jig, a load of 1 kg / cm 2 using steel wool # 0000, a stroke
- the scratched state of the test piece after 10 cm, speed 20 cm / sec, and reciprocating 200 times was visually observed, and scratch resistance was evaluated according to the following criteria.
- ⁇ 5 or more scratches are attached, but the entire test piece film is not damaged.
- X The test piece film is scratched.
- test piece film obtained above was cut into a 1 ⁇ 5 cm rectangle, and the cured film of the test piece film was fixed to the glass plate with a double-sided tape, and an automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd. was used. The contact angle of 4 to 4.5 ⁇ L of purified water was measured.
- Example 2 The non-volatile content was 40 as in Example 1 except that the 20% by mass solution of the fluorine compound (B-1) used in Example 1 was changed to 5 parts by mass (1 part by mass as the fluorine compound (B-1)).
- a mass% active energy ray-curable composition (2) was prepared. Using the obtained active energy ray-curable composition (2), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
- Example 4 The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 was 287.5 parts by mass to 187.5 parts by mass (75 as reactive silica (C1-1)).
- An active energy ray-curable composition (4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the content was changed to (parts by mass). Using the obtained active energy ray-curable composition (4), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
- Composition (R1) Active energy ray curable having a nonvolatile content of 40% by mass, as in Example 1, except that the reactive silica (C1-1) and non-reactive silica (C2-1) used in Example 1 were not blended.
- Composition (R1) was prepared. Using the obtained active energy ray-curable composition (R1), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
- Example 3 The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 is 287.5 parts by mass to 200 parts by mass (200 parts by mass as reactive silica (C1-1)).
- the active energy ray-curable composition (R3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the non-reactive silica (C2-1) was not added. Using the obtained active energy ray-curable composition (R3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
- Example 4 The blending amount of the non-reactive silica (C2-1) methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass used in Example 1 is 312.5 parts by mass to 500 parts by mass (200 as non-reactive silica (C2-1)).
- the active energy ray-curable composition (R4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the reactive silica (C1-1) was not blended. Using the obtained active energy ray-curable composition (R4), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
- Table 1 shows the compositions and evaluation results of the active energy ray-curable compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 described above.
- the compositions in Table 1 are all described in terms of non-volatile content, and for urethane acrylates (A1-1) to (A1-3), the blending amounts including PE4A are described.
- the active energy ray-curable compositions of Examples 1 to 4 of the present invention have no problem in appearance as a coating agent, and there is no problem in the appearance of the cured coating film. I was able to confirm. It was also confirmed that the active energy ray-curable composition of the present invention has low curl after curing and high curl resistance. Furthermore, it was confirmed that the cured coating film surface of the active energy ray-curable composition of the present invention has high pencil hardness and excellent scratch resistance, pencil hardness, antifouling property and slipperiness.
- Comparative Example 1 is an example of an active energy ray-curable composition that does not use both the reactive silica (C1) and the non-reactive silica (C2) used in the present invention, but the pencil hardness is not sufficient. Was confirmed.
- Comparative Example 2 is an example of an active energy ray-curable composition using a fluorine compound other than the fluorine compound (B) used in the present invention, but it can be confirmed that pencil hardness, scratch resistance, and slipperiness are not sufficient. It was.
- Comparative Example 3 is an example of an active energy ray-curable composition that does not use the non-reactive silica (C2) used in the present invention, but the pencil hardness is insufficient, the curl after curing is large, and the curl resistance It was confirmed that it was not enough.
- Comparative Example 4 is an example of an active energy ray-curable composition that did not use the reactive silica (C1) used in the present invention, but it was confirmed that pencil hardness and scratch resistance were not sufficient.
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Abstract
Description
(1)ポリ(パーフルオロアルキレンエーテル)鎖の両末端にアリル基を有する化合物とヒドロシリル基を有するシクロポリシロキサン化合物とを白金系触媒存在下で反応させ、ポリ(パーフルオロアルキレンエーテル)鎖の両末端にシクロポリシロキサン構造を有する化合物を得る工程。
(2)(1)で得られた化合物とアリルオキシアルカノールとを白金系触媒存在下で反応させ、(1)で得られた化合物のシクロポリシロキサン構造部位に水酸基を付加する工程。
(3)(2)で付加した水酸基にイソシアネート基を有する(メタ)アクリレートを反応させ、(メタ)アクリロイル基を導入する工程。 Examples of the method for producing the fluorine compound (B) include a method for producing the fluorine compound (B) through the following steps (1) to (3).
(1) A compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain and a cyclopolysiloxane compound having a hydrosilyl group are reacted in the presence of a platinum-based catalyst to form both poly (perfluoroalkylene ether) chains. A step of obtaining a compound having a cyclopolysiloxane structure at the terminal.
(2) A step of reacting the compound obtained in (1) with allyloxyalkanol in the presence of a platinum-based catalyst and adding a hydroxyl group to the cyclopolysiloxane structure portion of the compound obtained in (1).
(3) A step of reacting a hydroxyl group added in (2) with a (meth) acrylate having an isocyanate group to introduce a (meth) acryloyl group.
(GPCの測定条件)
・サンプル濃度:0.5重量%(テトラヒドロフラン溶液)
・サンプル注入量:100μL
・溶離液:テトラヒドロフラン(THF)
・流速:1.0mL/min
・カラム温度(測定温度):40℃
・カラム:東ソー株式会社製「TSKgel GMHHR-H」
・検出器:示差屈折 The weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values.
(GPC measurement conditions)
Sample concentration: 0.5% by weight (tetrahydrofuran solution)
Sample injection volume: 100 μL
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
Column temperature (measurement temperature): 40 ° C
・ Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation
・ Detector: Differential refraction
撹拌機、ガス導入管、冷却管及び温度計を備えたフラスコに、ペンタエリスリトールトリアクリレート(以下、「PE3A」と略記する。)及びペンタエリスリトールテトラアクリレート(以下、「PE4A」と略記する。)の混合物(PE3A/PE4A=60/40(質量比))549.1質量部、ジブチル錫ジアセテート0.1質量部、ジブチルヒドロキシトルエン0.6質量部、p-メトキシフェノール0.1質量部及び酢酸ブチル160質量部を加え、空気を吹き込み、均一に混合しながら徐々に昇温した。60℃に達したところでヘキサメチレンジイソシアネート90.9質量部を加えた後、80℃で5時間反応させ、1分子中に6つのアクリロイル基を有するウレタンアクリレート(A1-1)を含む不揮発分80質量%溶液を得た。なお、この溶液には、不揮発分中にウレタンアクリレート(A1-1)の他にPE4Aが34.3質量%含まれる。 (Synthesis Example 1: Synthesis of urethane acrylate (A1-1))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, pentaerythritol triacrylate (hereinafter abbreviated as “PE3A”) and pentaerythritol tetraacrylate (hereinafter abbreviated as “PE4A”). 549.1 parts by weight of the mixture (PE3A / PE4A = 60/40 (mass ratio)), 0.1 part by weight of dibutyltin diacetate, 0.6 part by weight of dibutylhydroxytoluene, 0.1 part by weight of p-methoxyphenol and acetic acid 160 parts by mass of butyl was added, air was blown in, and the temperature was gradually raised while mixing uniformly. When the temperature reached 60 ° C., 90.9 parts by mass of hexamethylene diisocyanate was added, followed by reaction at 80 ° C. for 5 hours, and a non-volatile content containing urethane acrylate (A1-1) having 6 acryloyl groups in one molecule. % Solution was obtained. This solution contains 34.3% by mass of PE4A in addition to urethane acrylate (A1-1) in the nonvolatile content.
攪拌機、ガス導入管、冷却管及び温度計を備えたフラスコに、酢酸ブチル254質量部、イソホロンジイソシアネート222質量部、p-メトキシフェノール0.5質量部及びジブチル錫ジアセテート0.5質量部を仕込み、空気を吹き込みながら、70℃に昇温した後、PE3A及びPE4Aの混合物(PE3A/PE4A=75/25(質量比))795質量部を1時間かけて滴下した。滴下終了後、70℃で3時間反応させ、さらにイソシアネート基を示す2250cm-1の赤外線吸収スペクトルが消失するまで反応を行い、1分子中に6つのアクリロイル基を有するウレタンアクリレート(A1-2)を含む不揮発分80質量%溶液を得た。なお、この溶液には、不揮発分中にウレタンアクリレート(A1-2)の他にPE4Aが19.5質量%含まれる。 (Synthesis Example 2: Synthesis of urethane acrylate (A1-2))
A flask equipped with a stirrer, gas introduction tube, cooling tube and thermometer was charged with 254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate. The temperature was raised to 70 ° C. while blowing air, and then 795 parts by mass of a mixture of PE3A and PE4A (PE3A / PE4A = 75/25 (mass ratio)) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappears, thereby obtaining urethane acrylate (A1-2) having 6 acryloyl groups in one molecule. A non-volatile content 80% by mass solution was obtained. This solution contains 19.5% by mass of PE4A in addition to urethane acrylate (A1-2) in the nonvolatile content.
攪拌機、ガス導入管、冷却管及び温度計を備えたフラスコに、PE3A及びPE4Aの混合物(PE3A/PE4A=60/40(質量比))242質量部、p-メトキシフェノール0.23質量部、ジブチル錫ジラウレート0.13質量部及びメチルエチルケトン100質量部を仕込み、空気を吹き込みながら、75℃に昇温した後、ヘキサメチレンジイソシアネートの3量化物(イソシアヌレート体)(住化バイエルウレタン株式会社製「デスモジュールN3390BA」、不揮発分90質量%、NCO%:19.6、NCO当量:214g/eq.)107質量部及びメチルエチルケトン50質量部の混合溶液を2時間かけて滴下した。滴下終了後、75℃で4時間反応させ、さらにイソシアネート基を示す2250cm-1の赤外線吸収スペクトルが消失するまで反応を行い、1分子中に9つのアクリロイル基を有するウレタンアクリレート(A1-3)を含む不揮発分67.8質量%溶液を得た。なお、この溶液には、不揮発分中にウレタンアクリレート(A1-3)の他にPE4Aが28.6質量%含まれる。 (Synthesis Example 3: Synthesis of urethane acrylate (A1-3))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube and a thermometer, 242 parts by mass of a mixture of PE3A and PE4A (PE3A / PE4A = 60/40 (mass ratio)), 0.23 parts by mass of p-methoxyphenol, dibutyl After charging 0.13 parts by mass of tin dilaurate and 100 parts by mass of methyl ethyl ketone and raising the temperature to 75 ° C. while blowing air, a trimerized hexamethylene diisocyanate (isocyanurate) (manufactured by Sumika Bayer Urethane Co., Ltd.) Module N3390BA ”, 90% by mass of non-volatile content, NCO%: 19.6, NCO equivalent: 214 g / eq.) 107 parts by mass and 50 parts by mass of methyl ethyl ketone were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was reacted at 75 ° C. for 4 hours, and further reacted until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappeared, and urethane acrylate (A1-3) having 9 acryloyl groups in one molecule was obtained. A 67.8 mass% solution with a nonvolatile content was obtained. This solution contains 28.6% by mass of PE4A in addition to urethane acrylate (A1-3) in the nonvolatile content.
攪拌機及び冷却管を備えたフラスコに、乾燥窒素雰囲気下で、下記式(5)で表される両末端にアリル基を有するパーフルオロポリエーテル500質量部、m-キシレンヘキサフロライド700質量部及びテトラメチルシクロテトラシロキサン361質量部を仕込み、攪拌しながら90℃まで昇温した。ここに塩化白金酸/ビニルシロキサン錯体のトルエン溶液0.442質量部(Pt単体として1.1×10-6モル含有。)を仕込み、内温を90℃以上に維持したまま4時間攪拌した。1H-NMRスペクトルで原料のアリル基が消失したのを確認した後、溶剤や過剰のテトラメチルシクロテトラシロキサンを減圧留去し、活性炭処理を行うことで、下記式(6)で表される無色透明の液体であるパーフルオロポリエーテル化合物(1)を得た。 (Synthesis Example 4: Synthesis of Fluorine Compound (B-1))
In a flask equipped with a stirrer and a condenser, in a dry nitrogen atmosphere, 500 parts by mass of perfluoropolyether having allyl groups at both ends represented by the following formula (5), 700 parts by mass of m-xylene hexafluoride, 361 parts by mass of tetramethylcyclotetrasiloxane was charged, and the temperature was raised to 90 ° C. while stirring. 0.442 parts by mass of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 −6 mol as a simple substance of Pt) was added thereto, and the mixture was stirred for 4 hours while maintaining the internal temperature at 90 ° C. or higher. After confirming disappearance of the allyl group of the raw material by 1 H-NMR spectrum, the solvent and excess tetramethylcyclotetrasiloxane are distilled off under reduced pressure, and activated carbon treatment is performed. A perfluoropolyether compound (1) which was a colorless and transparent liquid was obtained.
合成例1で得られたウレタンアクリレート(A1-1)を含む溶液62質量部(ウレタンアクリレート(A1-1)32.6質量部、PE4A 17質量部を含む。)、合成例3で得られたウレタンアクリレート(A1-3)を含む溶液18.3質量部(ウレタンアクリレート(A1-3)8.9質量部、PE4A 3.5質量部を含む。)、PE4A及びPE3Aの混合物(PE4A/PE3A=60/40(質量比))38質量部、合成例4で得られたフッ素化合物(B-1)の20質量%溶液7.5質量部(フッ素化合物(B-1)として1.5質量部)、反応性コロイダルシリカ(日産化学工業株式会社製「MEK-AC-2140Z」、不揮発分40質量%のメチルエチルケトン分散液;以下「反応性シリカ(C1-1)」と略記する。)287.5質量部(反応性シリカ(C1-1)として115質量部)、非反応性コロイダルシリカ(日産化学工業株式会社製「MEK-ST40」、不揮発分40質量%のメチルエチルケトン分散液;以下「非反応性シリカ(C2-1)」と略記する。)312.5質量部(非反応性シリカ(C2-1)として125質量部)、光重合開始剤(BASFジャパン株式会社製「イルガキュア184」、1-ヒドロキシシクロヘキシルフェニルケトン;以下、「光重合開始剤(D-1)」と略記する。)10.9質量部及び光重合開始剤(BASFジャパン株式会社製「イルガキュア754」、オキシフェニル酢酸2-[2-オキソ-2-フェニルアセトキシエトキシ]エチルエステルとオキシフェニル酢酸2-(2-ヒドロキシエトキシ)エチルエステルとの混合物;以下、「光重合開始剤(D-2)」と略記する。)1.6質量部を均一に攪拌した後、メチルエチルケトンで希釈して、不揮発分40質量%の活性エネルギー線硬化性組成物(1)を調製した。 Example 1
62 parts by mass of the solution containing urethane acrylate (A1-1) obtained in Synthesis Example 1 (including 32.6 parts by mass of urethane acrylate (A1-1) and 17 parts by mass of PE4A), obtained in Synthesis Example 3 18.3 parts by mass of a solution containing urethane acrylate (A1-3) (8.9 parts by mass of urethane acrylate (A1-3), 3.5 parts by mass of PE4A), a mixture of PE4A and PE3A (PE4A / PE3A = 60/40 (mass ratio)) 38 parts by mass, 7.5 parts by mass of a 20% by mass solution of the fluorine compound (B-1) obtained in Synthesis Example 4 (1.5 parts by mass as the fluorine compound (B-1)) ), Reactive colloidal silica (“MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass; hereinafter abbreviated as “reactive silica (C1-1)”) .) 287.5 parts by mass (115 parts by mass as reactive silica (C1-1)), non-reactive colloidal silica (“MEK-ST40” manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass; Hereinafter, abbreviated as “non-reactive silica (C2-1)”) 312.5 parts by mass (125 parts by mass as non-reactive silica (C2-1)), photopolymerization initiator (“Irgacure” manufactured by BASF Japan Ltd.) 184 ”, 1-hydroxycyclohexyl phenyl ketone; hereinafter abbreviated as“ photopolymerization initiator (D-1) ”) 10.9 parts by mass and photopolymerization initiator (“ Irgacure 754 ”manufactured by BASF Japan Ltd., oxy Phenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) Mixture with ethyl ester; hereinafter abbreviated as “photopolymerization initiator (D-2)”) 1.6 parts by mass of the mixture was uniformly stirred and then diluted with methyl ethyl ketone to obtain an active energy having a nonvolatile content of 40% by mass. A linear curable composition (1) was prepared.
上記で得られた活性エネルギー線硬化性組成物(1)が、塗剤として利用可能か判断するために、目視で外観を観察して、下記の基準にしたがい塗剤外観を評価した。
○:白濁及び成分分離がない。
×:白濁又は成分分離がある。 [Evaluation of coating appearance]
In order to judge whether the active energy ray-curable composition (1) obtained above can be used as a coating, the appearance was visually observed, and the coating appearance was evaluated according to the following criteria.
○: There is no cloudiness or component separation.
X: There is cloudiness or component separation.
上記で得られた活性エネルギー線硬化性組成物(1)を、ポリエチレンテレフタレート製フィルム(東洋紡株式会社製「コスモシャインA4100」、厚さ100μm)の易接着処理面上にワイヤーバー(#40)を用いて塗布して、60℃で1分間乾燥後、酸素濃度5,000ppm以下の雰囲気下で紫外線照射装置(アイグラフィックス株式会社製「MIDN-042-C1」、ランプ:120W/cm、高圧水銀灯)を用いて、照射光量0.5J/cm2で紫外線を照射して、厚さ15μmの硬化塗膜(ハードコート層)を有する試験片フィルムを得た。 [Preparation of test piece film]
The active energy ray-curable composition (1) obtained above is coated with a wire bar (# 40) on the easy-adhesion treated surface of a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 μm). After applying for use and drying at 60 ° C. for 1 minute, an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp in an atmosphere having an oxygen concentration of 5,000 ppm or less. ) Was irradiated with ultraviolet rays at an irradiation light amount of 0.5 J / cm 2 to obtain a test piece film having a cured coating film (hard coat layer) having a thickness of 15 μm.
上記で得られた試験片フィルムの硬化塗膜の表面を目視で観察し、下記の基準にしたがい硬化塗膜外観を評価した。
○:塗布ムラ、塗布スジ、及びブツがない。
×:塗布ムラ、塗布スジ又はブツがある。 [Evaluation of appearance of cured coating film]
The surface of the cured coating film of the test piece film obtained above was visually observed, and the cured coating film appearance was evaluated according to the following criteria.
○: There are no coating unevenness, coating streaks, and irregularities.
X: There are coating unevenness, coating stripes or irregularities.
上記で得られた評価用フィルムを10cm角に切り取り、23℃、50%RHで一晩静置の後、カールした四隅の底面からの浮き上がりを計測し、下記の基準にしたがい耐カール性を評価した。
◎:四隅の浮き上がりの平均値が10mm未満である。
○:四隅の浮き上がりの平均値が10mm以上25mm未満である。
×:四隅の浮き上がりの平均値が25mm以上である。 [Evaluation of curling resistance]
The film for evaluation obtained above was cut into a 10 cm square, allowed to stand overnight at 23 ° C. and 50% RH, then measured for lifting from the bottom of the curled corners, and evaluated for curl resistance according to the following criteria. did.
(Double-circle): The average value of lifting of four corners is less than 10 mm.
A: The average value of the four corners is 10 mm or more and less than 25 mm.
X: The average value of lifting of four corners is 25 mm or more.
上記で得られた評価用フィルムの硬化塗膜表面について、JIS S 6006:2007に規定された鉛筆を用いて、JIS K 5600-5-4:1999に準じて、傷跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として測定した。 [Measurement of pencil hardness]
The hardest pencil that did not cause a scar in accordance with JIS K 5600-5-4: 1999, using the pencil specified in JIS S 6006: 2007 for the cured coating film surface of the evaluation film obtained above. Was measured as pencil hardness.
上記で得られた試験片フィルムを30cm×2cmの長方形に切り取り、平面摩擦試験機(株式会社東洋精機製作所製)に治具で固定し、スチールウール#0000を用いて荷重1kg/cm2、ストローク10cm、速度20cm/秒、往復200回実施後の試験片の傷付き状態を目視観察し、下記の基準にしたがい耐擦傷性を評価した。
◎:傷が付かない。
○:5本未満の傷が付く。
△:5本以上の傷が付くが、試験片フィルム全面には傷が付かない。
×:試験片フィルム全体に傷が付く。 [Evaluation of scratch resistance]
The test piece film obtained above is cut into a 30 cm × 2 cm rectangle, fixed to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a jig, a load of 1 kg / cm 2 using steel wool # 0000, a stroke The scratched state of the test piece after 10 cm, speed 20 cm / sec, and reciprocating 200 times was visually observed, and scratch resistance was evaluated according to the following criteria.
A: Not scratched.
A: Less than 5 scratches are attached.
Δ: 5 or more scratches are attached, but the entire test piece film is not damaged.
X: The test piece film is scratched.
上記で得られた試験片フィルムを1×5cmの長方形に切り、試験片フィルムの硬化塗膜を表側にして両面テープでガラス板に固定し、協和界面科学株式会社製の自動接触角計「DROMPAMSTER500」で精製水4~4.5μLの接触角を測定した。 [Measurement of water contact angle]
The test piece film obtained above was cut into a 1 × 5 cm rectangle, and the cured film of the test piece film was fixed to the glass plate with a double-sided tape, and an automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd. was used. The contact angle of 4 to 4.5 μL of purified water was measured.
上記で得られた試験片フィルムの硬化塗膜上に、三菱鉛筆株式会社製「ユニ・メディアックス(黒)」でインクを円状に塗布し、インクのはじき度合いを目視観察した。その観察結果から、下記の基準にしたがい防汚性を評価した。
5:インクを点状にはじく。
4:インクを点と線状にはじく。
3:インクを線状にはじく。
2:インクをわずかにはじく。
1:インクをはじかない。 [Evaluation of antifouling properties]
On the cured coating film of the test piece film obtained above, ink was applied in a circular shape with “Uni Mediax (black)” manufactured by Mitsubishi Pencil Co., Ltd., and the degree of ink repelling was visually observed. From the observation results, antifouling properties were evaluated according to the following criteria.
5: The ink is repelled.
4: The ink is repelled by dots and lines.
3: The ink is repelled linearly.
2: Slightly repel ink.
1: Does not repel ink.
上記で得られた試験片フィルムの硬化塗膜の表面をベンコット(旭化成せんい株式会社製)で擦った際の滑りやすさから、下記の基準にしたがい滑り性を評価した。
◎:よく滑る。
○:滑る。
△:滑りにくい。
×:滑らない。 [Evaluation of slipperiness]
From the slipperiness when the surface of the cured coating film of the test piece film obtained above was rubbed with Bencott (manufactured by Asahi Kasei Fibers Corporation), the slipperiness was evaluated according to the following criteria.
A: Glide well.
○: Slip.
Δ: Not slippery
×: Does not slip.
実施例1で用いたフッ素化合物(B-1)の20質量%溶液を5質量部(フッ素化合物(B-1)として1質量部)とした以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(2)を調製した。得られた活性エネルギー線硬化性組成物(2)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 (Example 2)
The non-volatile content was 40 as in Example 1 except that the 20% by mass solution of the fluorine compound (B-1) used in Example 1 was changed to 5 parts by mass (1 part by mass as the fluorine compound (B-1)). A mass% active energy ray-curable composition (2) was prepared. Using the obtained active energy ray-curable composition (2), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
実施例1で用いたPE4A及びPE3Aの混合物(PE4A/PE3A=60/40(質量比))に代えて、合成例2で得られたウレタンアクリレート(A1-2)を含む溶液23.8質量部(ウレタンアクリレート(A1-2)15.3質量部、PE4A 3.7質量部を含む。)、ならびにDPHA及びDPPAの混合物(DPHA/DPPA=60/40(質量比))19質量部とした以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(3)を調製した。得られた活性エネルギー線硬化性組成物(3)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 Example 3
Instead of the mixture of PE4A and PE3A used in Example 1 (PE4A / PE3A = 60/40 (mass ratio)), 23.8 parts by mass of the solution containing urethane acrylate (A1-2) obtained in Synthesis Example 2 (Including urethane acrylate (A1-2) 15.3 parts by mass, PE4A 3.7 parts by mass), and DPHA and DPPA mixture (DPHA / DPPA = 60/40 (mass ratio)) 19 parts by mass Prepared an active energy ray-curable composition (3) having a nonvolatile content of 40% by mass in the same manner as in Example 1. Using the obtained active energy ray-curable composition (3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
実施例1で用いた反応性シリカ(C1-1)の不揮発分40質量%のメチルエチルケトン分散液の配合量を287.5質量部から187.5質量部(反応性シリカ(C1-1)として75質量部)に変更した以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(4)を調製した。得られた活性エネルギー線硬化性組成物(4)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 Example 4
The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 was 287.5 parts by mass to 187.5 parts by mass (75 as reactive silica (C1-1)). An active energy ray-curable composition (4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the content was changed to (parts by mass). Using the obtained active energy ray-curable composition (4), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
実施例1で用いた反応性シリカ(C1-1)及び非反応性シリカ(C2-1)を配合しなかった以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(R1)を調製した。得られた活性エネルギー線硬化性組成物(R1)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 (Comparative Example 1)
Active energy ray curable having a nonvolatile content of 40% by mass, as in Example 1, except that the reactive silica (C1-1) and non-reactive silica (C2-1) used in Example 1 were not blended. Composition (R1) was prepared. Using the obtained active energy ray-curable composition (R1), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
実施例1で用いたフッ素化合物(B-1)の20質量%溶液に代えて、ポリ(パーフルオロアルキレンエーテル)鎖の片末端にアクリロイル基を有するフッ素化合物(ダイキン工業株式会社製「オプツールDAC-HP」、不揮発分20質量部;以下、「フッ素化合物(RB-1)」と略記する。)7.5質量部(フッ素化合物(RB-1)として1.5質量部)を用いた以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(R2)を調製した。得られた活性エネルギー線硬化性組成物(R2)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 (Comparative Example 2)
Instead of the 20 mass% solution of the fluorine compound (B-1) used in Example 1, a fluorine compound having an acryloyl group at one end of a poly (perfluoroalkylene ether) chain (“OPTOOL DAC-” manufactured by Daikin Industries, Ltd.) HP ”, 20 parts by mass of nonvolatile content; hereinafter abbreviated as“ fluorine compound (RB-1) ”) Except for using 7.5 parts by mass (1.5 parts by mass as fluorine compound (RB-1)) In the same manner as in Example 1, an active energy ray-curable composition (R2) having a nonvolatile content of 40% by mass was prepared. Using the obtained active energy ray-curable composition (R2), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
実施例1で用いた反応性シリカ(C1-1)の不揮発分40質量%のメチルエチルケトン分散液の配合量を287.5質量部から500質量部(反応性シリカ(C1-1)として200質量部)に変更し、非反応性シリカ(C2-1)を配合しなかった以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(R3)を調製した。得られた活性エネルギー線硬化性組成物(R3)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 (Comparative Example 3)
The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 is 287.5 parts by mass to 200 parts by mass (200 parts by mass as reactive silica (C1-1)). The active energy ray-curable composition (R3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the non-reactive silica (C2-1) was not added. Using the obtained active energy ray-curable composition (R3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
実施例1で用いた非反応性シリカ(C2-1)の不揮発分40質量%のメチルエチルケトン分散液の配合量を312.5質量部から500質量部(非反応性シリカ(C2-1)として200質量部)に変更し、反応性シリカ(C1-1)を配合しなかった以外は、実施例1と同様に、不揮発分40質量%の活性エネルギー線硬化性組成物(R4)を調製した。得られた活性エネルギー線硬化性組成物(R4)を用いて、実施例1と同様に、試験片フィルムの作製後、評価又は測定を行った。 (Comparative Example 4)
The blending amount of the non-reactive silica (C2-1) methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass used in Example 1 is 312.5 parts by mass to 500 parts by mass (200 as non-reactive silica (C2-1)). The active energy ray-curable composition (R4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the reactive silica (C1-1) was not blended. Using the obtained active energy ray-curable composition (R4), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
Claims (14)
- 活性エネルギー線硬化性化合物(A)、ポリ(パーフルオロアルキレンエーテル)鎖の両末端に2価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に2価の連結基を介して(メタ)アクリロイル基が結合した構造を有するフッ素化合物(B)、反応性シリカ(C1)、及び非反応性シリカ(C2)を含有することを特徴とする活性エネルギー線硬化性組成物。 A cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, and a divalent linking group is bonded to the cyclopolysiloxane structure. An active energy ray-curable composition comprising a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded thereto, reactive silica (C1), and non-reactive silica (C2).
- 前記活性エネルギー線硬化性化合物(A)が、脂肪族ポリイソシアネート(a1)と水酸基を有する(メタ)アクリレート(a2)とを反応させて得られた1分子中に4つ以上の(メタ)アクリロイル基を有するウレタン(メタ)アクリレート(A1)、及び1分子中に3つ以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレート(A2)である請求項1記載の活性エネルギー線硬化性組成物。 The active energy ray-curable compound (A) is obtained by reacting an aliphatic polyisocyanate (a1) with a (meth) acrylate (a2) having a hydroxyl group, and four or more (meth) acryloyl groups in one molecule. The active energy ray-curable composition according to claim 1, which is a urethane (meth) acrylate (A1) having a group and a polyfunctional (meth) acrylate (A2) having three or more (meth) acryloyl groups in one molecule. object.
- 前記脂肪族ポリイソシアネート(a1)が、ヘキサメチレンジイソシアネート、ノルボルナンジイソシアネート、イソホロンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)及びこれらの3量化物からなる群から選ばれる1種以上のポリイソシアネートである請求項2記載の活性エネルギー線硬化性組成物。 3. The aliphatic polyisocyanate (a1) is one or more polyisocyanates selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) and trimers thereof. The active energy ray-curable composition described.
- 前記(メタ)アクリレート(a2)が、ジペンタエリスリトールペンタ(メタ)アクリレート及びペンタエリスリトールトリ(メタ)アクリレートからなる群から選ばれる1種以上の(メタ)アクリレートである請求項2項記載の活性エネルギー線硬化性組成物。 The active energy according to claim 2, wherein the (meth) acrylate (a2) is at least one (meth) acrylate selected from the group consisting of dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate. A linear curable composition.
- 前記多官能(メタ)アクリレート(A2)の(メタ)アクリロイル基当量が、50~200g/eq.の範囲である請求項2記載の活性エネルギー線硬化性組成物。 The polyfunctional (meth) acrylate (A2) has a (meth) acryloyl group equivalent of 50 to 200 g / eq. The active energy ray-curable composition according to claim 2, which is in the range of
- 前記多官能(メタ)アクリレート(A2)が、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート及びペンタエリスリトールトリ(メタ)アクリレートからなる群から選ばれる1種以上の多官能(メタ)アクリレートである請求項2記載の活性エネルギー線硬化性組成物。 The polyfunctional (meth) acrylate (A2) is selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate and pentaerythritol tri (meth) acrylate. The active energy ray-curable composition according to claim 2, which is one or more polyfunctional (meth) acrylates.
- 請求項1~6のいずれか1項記載の活性エネルギー線硬化性組成物に、活性エネルギー線を照射して得られたことを特徴とする硬化物。 A cured product obtained by irradiating the active energy ray-curable composition according to any one of claims 1 to 6 with active energy rays.
- 請求項1~6のいずれか1項記載の活性エネルギー線硬化性組成物に、酸素濃度が5,000ppm以下のガス雰囲気下で、紫外線を照射することによって得られたことを特徴とする硬化物。 A cured product obtained by irradiating the active energy ray-curable composition according to any one of claims 1 to 6 with ultraviolet rays in a gas atmosphere having an oxygen concentration of 5,000 ppm or less. .
- 請求項1~6のいずれか1項記載の活性エネルギー線硬化性組成物の硬化塗膜を有することを特徴とする物品。 An article comprising a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 6.
- フィルム基材の少なくとも一面にハードコート層を有し、前記ハードコート層が請求項1~6のいずれか1項記載の活性エネルギー線硬化性組成物の硬化物からなることを特徴とするハードコートフィルム。 A hard coat comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises a cured product of the active energy ray-curable composition according to any one of claims 1 to 6. the film.
- ハードコート層の厚さが1~20μmであり、基材の厚さが50~200μmである請求項10記載のハードコートフィルム。 11. The hard coat film according to claim 10, wherein the hard coat layer has a thickness of 1 to 20 μm and the base material has a thickness of 50 to 200 μm.
- 請求項10記載のハードコートフィルムの一面に粘着剤層を有することを特徴とする保護フィルム。 A protective film comprising an adhesive layer on one side of the hard coat film according to claim 10.
- 粘着剤層の厚さが5~50μmである請求項12記載の保護フィルム。 The protective film according to claim 12, wherein the pressure-sensitive adhesive layer has a thickness of 5 to 50 µm.
- 携帯電子端末の画像表示部の保護に使用される請求項12記載の保護フィルム。 The protective film according to claim 12, which is used for protecting an image display unit of a portable electronic terminal.
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